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US2006216A - Inhibitor - Google Patents

Inhibitor Download PDF

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Publication number
US2006216A
US2006216A US657844A US65784433A US2006216A US 2006216 A US2006216 A US 2006216A US 657844 A US657844 A US 657844A US 65784433 A US65784433 A US 65784433A US 2006216 A US2006216 A US 2006216A
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United States
Prior art keywords
bath
pickling
cleaning
acid
loss
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Expired - Lifetime
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US657844A
Inventor
Macarthur Arthur
Hailwood Anthony James
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication date
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors

Definitions

  • This invention relates to the production of pickling or cleaning baths which display protective action on the metal of crude ferrous metal surfaces, whereby the oxide and scale are selectively dissolved without substantial loss of free metal. Furthermore these baths have the property of forming a surface foam.
  • the acid pickling or cleaning bath which may consist of an aqueous solution of sulphuric acid o hydrochloric acid, or othernon-oxi'dizingacid, a long chain alkyl quaternaiy a'lnmoniunicompound.
  • long chain alkyl quaternary ammonium compound we mean a compound containing a quaternary ammonium grouping, and a long chain alkyl radical, thatigap alkyl r groupl 9 not less than-si r cnat ms.
  • a pickling bath is prepared by mixing 1.75 parts of octadecyl-pyridinium bromide with 100,000 parts of a 7% solution of sulphuric acid in water and heating to a temperature of about 90 C. If sheet iron, with an oxidized or scaly surface, is immersed in this bath the impurity is readily removed leaving a clean metallic surface. During this process of pickling a foam is formed on the surface. When previously de-scaled and cleaned, sheet iron is immersed for five minutes in a similar bath, the metallic loss which results amounts to 0.31% by weight, whereas similar treatment in a free acid bath not containing the octadecyl-pyridinium bromide results in a loss of 2.53% by weight.
  • Example 2 2 parts of cetyltrimethylammonium bromide are dissolved in 100,000 parts of 7% sulphuric acid at C.
  • descaled sheet iron was immersed for 5 minutes in such a bath and the metallic loss which resulted was 0.195% whilst similar treatment of the same sheet iron without the use of an inhibitor brought about a metallic loss of 1.16%.
  • Example 3 A pickling bath is prepared by mixing 1.75% parts of octadecyltrimethylammonium bromide with 100,000 parts of a 7% solution of sulphuric acid in water and heating to a temperature of about C. If sheet iron, with an oxidized or scaly surface is immersed in this bath the impurity is readily removed leaving a clean metallic surface. During this process of pickling a foam is formed on the surface. When previously descaled and cleaned sheet iron is immersed for five minutes in a similar bath, the metallic loss which results amounts to 0.122% by weight, whereas similar treatment in a free acid bath not containing the octadecyltrimethylammonium bromide results in a loss of 1.16% by weight.
  • Example 4 1 part dodecyl pyridinium bromide is dissolved in 8000 parts of 4.8% hydrochloric acid at 20-24 C.
  • the metallic loss resulting was 0.0665% whilst similar treatment of the same iron without the use of an inhibitor brought about a metallic loss of 2.14%.
  • cetylpyridinium bromide possesses an inhibiting efficiency ranging from 99.5% for a concentration of 0.5% to 92.8% efflciency for a concentration of 0.001%.
  • cetyl-trimethyl ammonium bromide were 93.3% and 89.2% respectively.
  • a cleaning and pickling bath for metals comprising a dilute, non-oxidizing acid and a small amount of an Organic MQIPFFXJQPFQQEQYK moniuincompound.
  • a cleaning and pickling bath for metals comprising a dilute, non-oxidizing acid, and a small amount of an organic quaternary-cetyl ammonium compound.
  • a cleaning and pickling bath for metal comprising a dilute, non-oxidizing acid, and a small amount of a cetyl-pyridinium compound.
  • a cleaning and picking bath for metals comprising a dilute, non-oxidizing acid and a small amount of a compound of the formula:
  • R1 is a long chain alkyl radical of not less than 6 carbon atoms
  • X is a hydroxyl or acid group
  • R2, R3 and R4 are alkyl radicals or the valences at R2, R3 and R4 are satisfied by including N in a pyridine ring.
  • a cleaning and pickling bath for metals comprising a dilute, non-oxidizing acid and a small amount of a compound selected from the group consisting of organic quaternary-octadecyl ammonium compounds and quaternary-cetyl ammonium compounds.
  • R1 of the formula is a long chain alkyl radical of from 12 to 18 inclusive carbon atoms.
  • R1 of the formula is a long chain alkyl radical of from 12 to 18 inclusive carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

1 4 8 atented June 25, i935 2 52. COMPOSITIONS,
UNIlED STATES Examin PATENT OFFICE INHIBITOR Arthur Macarthur and Anthony James Hailwood, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application February 21, 1933, Serial No. 657,844. In Great Britain February 12 Claims.
This invention relates to the production of pickling or cleaning baths which display protective action on the metal of crude ferrous metal surfaces, whereby the oxide and scale are selectively dissolved without substantial loss of free metal. Furthermore these baths have the property of forming a surface foam.
According to our invention we add to the acid pickling or cleaning bath, which may consist of an aqueous solution of sulphuric acid o hydrochloric acid, or othernon-oxi'dizingacid, a long chain alkyl quaternaiy a'lnmoniunicompound.
By the term long chain alkyl quaternary ammonium compound we mean a compound containing a quaternary ammonium grouping, and a long chain alkyl radical, thatigap alkyl r adical 9 not less than-si r cnat ms.
Compounds of this type are obtained from the higher alcohols and are exemplified by cetylpyridinium bromide, cetyl-trimethyl-ammonium hydroxide, octadegyl-pyridinium, haloggnigigf'.the free bases or other salts thereof.
The invention is illustrated but not limited by the following example in which the parts are by weight.
Ezample 1 A pickling bath is prepared by mixing 1.75 parts of octadecyl-pyridinium bromide with 100,000 parts of a 7% solution of sulphuric acid in water and heating to a temperature of about 90 C. If sheet iron, with an oxidized or scaly surface, is immersed in this bath the impurity is readily removed leaving a clean metallic surface. During this process of pickling a foam is formed on the surface. When previously de-scaled and cleaned, sheet iron is immersed for five minutes in a similar bath, the metallic loss which results amounts to 0.31% by weight, whereas similar treatment in a free acid bath not containing the octadecyl-pyridinium bromide results in a loss of 2.53% by weight.
Example 2 2 parts of cetyltrimethylammonium bromide are dissolved in 100,000 parts of 7% sulphuric acid at C. In comparative experiments descaled sheet iron was immersed for 5 minutes in such a bath and the metallic loss which resulted was 0.195% whilst similar treatment of the same sheet iron without the use of an inhibitor brought about a metallic loss of 1.16%.
Example 3 A pickling bath is prepared by mixing 1.75% parts of octadecyltrimethylammonium bromide with 100,000 parts of a 7% solution of sulphuric acid in water and heating to a temperature of about C. If sheet iron, with an oxidized or scaly surface is immersed in this bath the impurity is readily removed leaving a clean metallic surface. During this process of pickling a foam is formed on the surface. When previously descaled and cleaned sheet iron is immersed for five minutes in a similar bath, the metallic loss which results amounts to 0.122% by weight, whereas similar treatment in a free acid bath not containing the octadecyltrimethylammonium bromide results in a loss of 1.16% by weight.
Example 4 1 part dodecyl pyridinium bromide is dissolved in 8000 parts of 4.8% hydrochloric acid at 20-24 C. When as above descaled sheet iron was immersed for 15 hours in such a bath the metallic loss resulting was 0.0665% whilst similar treatment of the same iron without the use of an inhibitor brought about a metallic loss of 2.14%.
Testing the eflicieney of such compounds by the loss of weight method we found that cetylpyridinium bromide possesses an inhibiting efficiency ranging from 99.5% for a concentration of 0.5% to 92.8% efflciency for a concentration of 0.001%. For this same range of concentrations 'the efiiciency ratings of cetyl-trimethyl ammonium bromide were 93.3% and 89.2% respectively.
In both instances the baths were covered by a tenacious foam.
We claim:
1. A cleaning and pickling bath for metals comprising a dilute, non-oxidizing acid and a small amount of an Organic MQIPFFXJQPFQQEQYK moniuincompound.
A cleaning and pickling bath for metals comprising a dilute, non-oxidizing acid, and a small amount of an organic quaternary-cetyl ammonium compound.
3. A cleaning and pickling bath for metal comprising a dilute, non-oxidizing acid, and a small amount of a cetyl-pyridinium compound.
4. In a process of cleaning and pickling metal articles the step of treating said articles with a 6. In a process of cleaning and pickling metal articles the step of treating said articles with a bath comprising a dilute, non-oxidizing acid and a small amount of a cetyl-pyridinium compound.
7. A cleaning and picking bath for metals comprising a dilute, non-oxidizing acid and a small amount of a compound of the formula:
wherein R1 is a long chain alkyl radical of not less than 6 carbon atoms, X is a hydroxyl or acid group, and wherein R2, R3 and R4 are alkyl radicals or the valences at R2, R3 and R4 are satisfied by including N in a pyridine ring.
8. A cleaning and pickling bath for metals comprising a dilute, non-oxidizing acid and a small amount of a compound selected from the group consisting of organic quaternary-octadecyl ammonium compounds and quaternary-cetyl ammonium compounds.
9. In a process of cleaning and pickling metal articles the step of treating said articles with a bath comprising a dilute, non-oxidizing acid and a small amount of wherein R1 is a long chain alkyl radical of not less than 6 carbon atoms, X is a hydroxyl or acid group, and wherein R2, R3 and R4 are alkyl radicals or the valences of R2, R3 and R4 are satisfied by including N in a pyridine ring.
10. In a process of cleaning and pickling metal articles the step of treating said articles with a bath comprising a dilute, non-oxidizing acid and a small amount of a compound selected from the group consisting of organic quaternary-octadecyl ammonium compounds and quatemary-cetyl ammonium compounds.
11. The cleaning and pickling bath of claim 7 in which R1 of the formula is a long chain alkyl radical of from 12 to 18 inclusive carbon atoms.
12. The process of claim 9 in which R1 of the formula is a long chain alkyl radical of from 12 to 18 inclusive carbon atoms.
ARTHUR MACARTI-IUR. ANTHONY JAMES HAILWOOD.
US657844A 1932-02-26 1933-02-21 Inhibitor Expired - Lifetime US2006216A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5855/32A GB397553A (en) 1932-02-26 1932-02-26 Acid pickling baths

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2459119A (en) * 1946-09-27 1949-01-11 Hooker Electrochemical Co Corrosion retarder
US2505785A (en) * 1945-09-17 1950-05-02 Howard R Moore Method of producing a corrosion inhibitive coating on ferrous metals
US2617771A (en) * 1946-09-27 1952-11-11 Hooker Electrochemical Co Corrosion retarder
US2941949A (en) * 1957-05-14 1960-06-21 Amchem Prod Acid baths for cleaning and pickling metal
US2947703A (en) * 1958-07-16 1960-08-02 Nalco Chemical Co Process of inhibiting corrosion of ferrous metals in contact with aqueous solutions of acids
US3033796A (en) * 1957-01-23 1962-05-08 Swift & Co Acid pickling bath containing inhibitor and method of treating ferrous metals
US3047510A (en) * 1957-06-05 1962-07-31 Armour & Co Corrosion inhibiting compositions and process
US3146208A (en) * 1960-12-29 1964-08-25 Monsanto Co Corrosion inhibition
US3197301A (en) * 1963-01-04 1965-07-27 Fmc Corp Liquid fertilizers inhibited against corrosion
US3260673A (en) * 1964-01-27 1966-07-12 Monsanto Co Corrosion inhibited phosphoric acid composition
US3323862A (en) * 1963-06-25 1967-06-06 Fmc Corp Corrosion inhibition
US3345296A (en) * 1964-02-28 1967-10-03 Fmc Corp Corrosion inhibition
EP0519594A1 (en) * 1991-05-29 1992-12-23 Petrolite Corporation Corrosion inhibition in highly acidic environments by use of pyridine salts in combination with certain cationic surfactants
US20080268149A1 (en) * 2000-02-02 2008-10-30 Djamschid Amirzadeh-Asl Barium sulfate, process for its preparation, and its use

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955087A (en) * 1957-04-08 1960-10-04 Arthur D Berryman Compositions and methods for treating metal surfaces

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2505785A (en) * 1945-09-17 1950-05-02 Howard R Moore Method of producing a corrosion inhibitive coating on ferrous metals
US2459119A (en) * 1946-09-27 1949-01-11 Hooker Electrochemical Co Corrosion retarder
US2617771A (en) * 1946-09-27 1952-11-11 Hooker Electrochemical Co Corrosion retarder
US3033796A (en) * 1957-01-23 1962-05-08 Swift & Co Acid pickling bath containing inhibitor and method of treating ferrous metals
US2941949A (en) * 1957-05-14 1960-06-21 Amchem Prod Acid baths for cleaning and pickling metal
US3047510A (en) * 1957-06-05 1962-07-31 Armour & Co Corrosion inhibiting compositions and process
US2947703A (en) * 1958-07-16 1960-08-02 Nalco Chemical Co Process of inhibiting corrosion of ferrous metals in contact with aqueous solutions of acids
US3146208A (en) * 1960-12-29 1964-08-25 Monsanto Co Corrosion inhibition
US3197301A (en) * 1963-01-04 1965-07-27 Fmc Corp Liquid fertilizers inhibited against corrosion
US3323862A (en) * 1963-06-25 1967-06-06 Fmc Corp Corrosion inhibition
US3260673A (en) * 1964-01-27 1966-07-12 Monsanto Co Corrosion inhibited phosphoric acid composition
US3345296A (en) * 1964-02-28 1967-10-03 Fmc Corp Corrosion inhibition
EP0519594A1 (en) * 1991-05-29 1992-12-23 Petrolite Corporation Corrosion inhibition in highly acidic environments by use of pyridine salts in combination with certain cationic surfactants
US5336441A (en) * 1991-05-29 1994-08-09 Petrolite Corporation Corrosion inhibition in highly acidic environments by use of pyridine salts in combination with certain cationic surfactants
US20080268149A1 (en) * 2000-02-02 2008-10-30 Djamschid Amirzadeh-Asl Barium sulfate, process for its preparation, and its use
US7776149B2 (en) * 2000-02-02 2010-08-17 Sachtleben Chemie Gmbh Barium sulfate, process for its preparation, and its use

Also Published As

Publication number Publication date
GB397553A (en) 1933-08-28

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